The purpose of this study was to determine the optimal firing condition and composition for Al2TiO5 crystal, which is suitable for stable coloration in glazes at high temperatures, using Cr2O3 as chromophore for the synthesis of Al2TiO5 system pigments. Al2TiO5 has a high refractive index and good solubility of chromophore in the Al2TiO5 lattice, making this structure a good candidate for the development of new ceramic pigments. Pigments were synthesized by using Al2O3 and TiO2 mainly. Various amounts of Cr2O3 such as 0.01, 0.02, 0.03, 0.04 and 0.05 mole were also added. Each compound was synthesized at 1300oC, 1400oC, and 1500oC for 2 hours and cooled naturally. The crystal structure, solubility limit, and color of the synthesized pigments were analyzed by XRD, SEM, Raman spectroscopy, UV and UV-vis. The changes in color as the result of applying 6 wt% of the synthesized pigments to lime barium glaze were expressed as CIE-L*a*b* values. A Cr2O3 0.03 mole doped Al2TiO5 brown pigment was successfully synthesize at 1400oC, and the values of CIE-L*a*b* parameters were L* = 44.62, a* = 3.10, and b* = 17.25. In the case of the pigment synthesized at 1500oC, the brown color was obtained at 0.01 mole and 0.02 mole Cr2O3, and the CIE-L*a*b* values were 55.34, 1.73, 28.64, and 49.39, 0.51, 21.33, respectively. At 1500oC, the maximum limit of solid solution was 0.03 mole Cr2O3. The glazed sample showed green color, and the values of the CIEL*a*b* parameters were L* = 45.69, a* = .0.98, and b* = 20.38.